title: Inclusion complexes of cypermethrin and permethrin with monochlorotriazinyl-beta-cyclodextrin: a combined spectroscopy, TG/DSC and DFT study.
abstract: The suitable size hydrophobic cavity and monochlorotriazinyl group as a reactive anchor make MCT-β-CD to be widely used in fabric finishing. In this paper, the inclusion complexes of monochlorotriazinyl-beta-cyclodextrin (MCT-β-CD) with cypermethrin (CYPERM) and permethrin (PERM) are synthesized and analyzed by TG/DSC, FT-IR and Raman spectroscopy. TG/DSC reveals that the decomposed temperatures of inclusion complexes are lower by 25-30 °C than that of physical mixtures. DFT calculations in conjunction with FT-IR and Raman spectral analyses are used to study the structures of MCT-β-CD and their inclusion complexes. Four isomers of trisubstituted MCT-β-CD are designed and DFT calculations reveal that 1,3,5-trisubstituted MCT-β-CD has the lowest energy and can be considered as main component of MCT-β-CD. The ground-state geometries, vibrational wavenumbers, IR and Raman intensities of MCT-β-CD and their inclusion complexes were calculated at B3LYP/6-31G (d) level of theory. Upon examining the optimized geometry of inclusion complex, we find that the CYPERM and PERM are inserted into the toroid of MCT-β-CD from the larger opening. The band at 1646 cm(-1) in IR and at 1668 cm(-1) in Raman spectrum reveals that monochloroazinyl group of MCT-β-CD exists in ketone form but not in anion form. The noticeable IR and Raman shift of phenyl reveals that these two benzene rings of CYPERM and PERM stays inside the cavity of MCT-β-CD and has weak interaction with MCT-β-CD. This spectroscopy conclusion is consistent with theoretical predicted structure.
authors.affiliation: School of Chemistry and Chemical engineering, Wuhan Textile University, 430073 Wuhan, China.
authors.forename: Qi
authors.initials: Q
authors.lastname: Yao
authors.forename: Bin
authors.initials: B
authors.lastname: You
authors.forename: Shuli
authors.initials: S
authors.lastname: Zhou
authors.forename: Meng
authors.initials: M
authors.lastname: Chen
authors.forename: Yujiao
authors.initials: Y
authors.lastname: Wang
authors.forename: Wei
authors.initials: W
authors.lastname: Li
mesh_terms: D004055:Differential Thermal Analysis; D008958:Models, Molecular; D015394:Molecular Structure; D026023:Permethrin / Q000737:chemistry*; D011722:Pyrethrins / Q000737:chemistry*; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D014732:Vibration; D047392:beta-Cyclodextrins / Q000737:chemistry*
chemical_list: D011722:Pyrethrins; D047392:beta-Cyclodextrins; C017160:cypermethrin; D026023:Permethrin; C031215:betadex
keywords: DFT; FT-IR; MCT-β-CD inclusion complex; Raman; TG/DSC